Cyclic ketones of the acenaphthene series and process of preparing them



Patented June 13, 1933 UNITED PAT NT "OFFICE WILHELM ncxnn'r, summon sienna, AND Hemmer: GREUNE, or FRANKFonT-om THE-MAIN-HOCHST, AND'GERHARID LANGBEIN, or HOFHEIM IN TAUNUS, GERMANY, ASSIGNORS '10 GENERAL Animus wons, Inc, on NEW some, n. Y., A CORPORA- TION OF DELAWARE CYGLIC KETONES OF THE ACENPHTHENE SERIES AND PROCESS OF PREPARING THEM v No Drawing. Application filed August 2 7 1930, Serial. in. 478,311, and in German September 25, 1929.

The present invention relates to cyclic ketones of the acenaphtheneseries and process of preparingthem.

We have found that cyclic ketones of the acenaphthene series of the following probae v I mg them in the name of Wilhelm Eckert,

ble formula wherein the naphthalene nucleus mayvcontain substituents are obtainedv by causing aluminium chloride to act upon a; compound of the following formula stance, alkaliL metal-hydroxide the corre-;

sponding bases'are obtained in a free state. The cyanoeacetyloiacenaphthenesoxused 1. as

starting materials may, for instance, be obtained according to the process described in the copending U. S. Patent application Serial No. 478,310 for substitution products of aromatic compounds and process of prepar- Heinrich Sieber and Heinrich Greune.

Thenew cyclic'ketones are Valuable intermediate products for the manufacture of Vat dyestuffs. 4 In order to prepare the new cyclic ketones it is sometimes unnecessary to isolate the cyano-acetyl acenaphthenes used as starting materials. It is rather possible to prepare these cyclic ketones of acenaphthene or its derivatives by condensation of cyanoacetyl chloride with acenaphthene or a derivative thereof and transformation of the condensationproducts into the corresponding cyclic ketones by means of an aluminum chloride in a single operation, if these reactions are carried out in an indifferent solvent, as, for instance, tetrachloro-ethane.

- This procedure simplifies the process 1 hitherto k110wn.'

The following examplesserve to illustrate theinvention, but they are not intended to limit itv thereto, the parts are by weight:

, 10 parts of the product of the'fol-' lowing formula v N to [aluminium chloride and 10 parts of sodium sol 5 Hz C CH2 separates. It crystallizes from chloro-benzene in the form of yellow prisms.

(2) 50 partsv of the said product from cyano-acetyl chloride and acenaphthene are melted together with 200 parts of aluminium chloride at a temperature of about 140 C.

ice water, filtered by suction and washed until neutral. The cyclic ketone is obtained with the same yield and purity as by the process of Example 1.

(3) parts of the said product from 'cyano-acetyl chloride and acenaphthene are dissolved in 300 parts by volume of tetrachlorethane and the solution is heated to a temperature of about 140 C. At this temperature 90 parts of aluminium chloride are introduced. After a short time the condensation product is decomposed by means of ice and hydrochloric acid and the solvent is distilled with aid of steam. The residue is filtered by suction, washed until neutral and dried. The properties of the cyclic ketone thus obtained are identical with those of the products obtained as described in EX- amples 1 and 2. Instead of tetrachloroethane, chloro-benzenc may also be used as solvent.

(4) parts of 1-chloro-cyan0acetylacenaphthene of one of the following formulae:

are gradually introduced at 120 G. into a suspension of 80 parts of aluminium chloride tain chlorine as a substituent at a tempera-1 After 510 minutes the melt is poured into' temperature is maintained for about 1 hour. The condensation product is decomposed by means of ice and the solvent is distilled with aid of steam. The residue is filtered with suction, washed with a solution of sodium chloride until neutral and dried. The hydrochloride of the ketimide of l-chloroacenaphth-peri-indandion of one of the following formulae:

has a yellow coloration is soluble in hot water. It dissolves in concentrated sulfuric acid to a yellow solution having a green fluorescence. It melts at above 300 C.

(5) 48 parts of cyanoacetic acid are dissolved in 100 parts by volume of tetrachloro-ethane and transformed into the acid chloride by means of 120 parts of phosphorus pentachloride. At a temperature of C. 180 parts of aluminium chloride are added to this solution which is then heated to 40 C. At this temperature 55 parts of acenaphthene are gradually entered and the whole is further heated to C. C. for one hour. When theevolution of hydrochloric acid is finished the solution is heated to aluminium chloride to act upon a compound of the following formula 7 NEC do li fa wherein the naphthalene nucelus may con- 5 in 120 parts of dry chloro-benzene and the ture between about110 CL and about 160 C.

2. The process which comprises causing wherein one of the Xs stands for'hydrogen, aluminium chloride to act upon a compound the other X stands for chlorine, at a temof the following formula perature of about 120 C. in the presence of chlorobenzene.

EEO-CH2 7. As new products, the compounds of the following probable formula HgC-C BT2 NEG to ll H2 wherein the naphthalene nucelus may contain chlorine as a substituent at a tempera- C0 ture between about 110 C. and about 160 C. in the presence of an inert diluent. V "f 3. The process which comprises causing H2 aluminum chloride to act upon a compound of the following formula H2C OH2 wherein the naphthalene nucleus may contam chlorlne as a substituent.

8. As new products, the compounds of the following probable formula wherein one of the Xs stands for hydrogen, the other X for hydrogen or chlorine at a temperature between about 110 C. and about 160 C.

4. The process which comprises causing HN=G CO aluminium chloride to act upon a compound 1 of the following formula HzCOH2 i 1 wherein one of the Xs stands for hydro- X X gen or chlorine, the other for hydrogen, forming with hydrochloric, acid yellowish salts which melt above 300 C. and dissolving in concentrated sulfuric acid to a yellow solution showing a strong green CH2 fluorescence.

9. As a new product, the compound of l f th t d f d W18I'G111 one o e Xs s an s or by rogen, the fo w g p obab e formula the other X for hydrogen or chlorine, at a temperature between about 110 C. and about 160 C. in the presence of an inert organic diluent.

5. The process which comprises causing aluminium chloride to act upon S-cyanoacetyl-acenaphthene at a temperature of about 140 C. in the presence of tetrachloroethane,

6. The process which comprises causing aluminium chloride to act upon a compound of the following formula Bic- UE:

o EH1 HZCCH2 1 1 crystallizing from chloro-benzene in the X form of yellow prisms yielding with hydrochloric acid an orange-yellow salt which melts above 300 C. and dissolves in hot NEG to water to a yellow solution and in concentrated sulfuric acid to a yellow solution showing a strong green fluorescence.

10. As a new product, the compound of the following 'probable formula HQC CHQ wherein one of the Xs stands for chlorine, the other X stands for hydrogen, forming with hydrochloric acid a yellow salt which melts above 300C. and dissolves in hot water and in concentrated sulfuric acid to a yellow solution showing a green fluorescence.

In testimony whereof, we afiix our signatures.

WILHELM ECKERT. HEINRICH SIEBER. HEINRICH GREUNE. GERHARD LANGBEIN. 

